The invention relates to novel 4-hydroxyindole derivatives comprising at least one cationic group Z, Z being selected from quaternized aliphatic chains, aliphatic chains containing at least one quaternized saturated ring, and aliphatic chains containing at least one quaternized unsaturated ring, to their use as a coupler for the oxidation dyeing of keratinous fibers, to the dyeing compositions comprising them, and to the methods of oxidation dyeing which employ them.
It is known to dye keratinous fibers, and especially human hair, with dyeing compositions comprising oxidation dye precursors, especially para-phenylenediamines, ortho- or para-aminophenols, and heterocyclic compounds, such as diaminopyrazole derivatives, which are referred to generally as oxidation bases. The oxidation dye precursors or oxidation bases are colourless or slightly coloured compounds which, when combined with oxidizing products, have the capacity to give rise to coloured compounds and dyes by virtue of a process of oxidative condensation.
It is also known that the shades obtained with these oxidation bases can be varied by combining them with couplers or coloration modifiers, the latter being selected in particular from aromatic meta-diamines, meta-aminophenols, meta-diphenols and certain heterocyclic compounds such as, for example, indole couplers.
The variety of molecules employed as oxidation bases and couplers makes it possible to obtain a wide range of colours.
The so-called permanent coloration obtained by virtue of these oxidation dyes should, moreover, satisfy certain conditions. Hence it should have no toxicological drawbacks, should allow shades of the desired intensity to be obtained, and should have good resistance to external agents (light, inclement weather, washing, permanent-waving, perspiration and friction).
The dyes should also allow white hair to be covered and, finally, they should be as unselective as possible; in other words, they should allow the smallest possible differences in coloration to be produced over the entire length of a single keratinous fibre, which may in fact be sensitized (i.e. damaged) differently between its tip and its root.
The inventors have now discovered, in a manner totally unexpected and surprising, that a novel class of 4-hydroxyindole derivatives of formula (I) defined below, containing at least one cationic group Z, Z being selected from quaternized aliphatic chains, aliphatic chains containing at least one quaternized saturated ring, and aliphatic chains containing at least one quaternized unsaturated ring, are suitable for use as a coupler for oxidation dyeing and that, furthermore, they make it possible to obtain dyeing compositions which lead to intense colorations in a very wide range of shades and have excellent properties of resistance to the various treatments which the keratinous fibers may undergo. Finally, these compounds have been found to be readily synthesizable.
It is these discoveries which form the basis of the present invention.
The invention therefore provides, firstly, 4-hydroxyindole derivatives of formula (I) below and their addition salts with an acid: 
in which:
R1 represents a hydrogen atom; a group Z; a C1-C4 alkyl radical; a C1-C4 monohydroxyalkyl radical; a C2-C4 polyhydroxyalkyl radical; a (C1-C4 alkoxy)-C1-C4 alkyl radical; a hydroxy(C1-C4 alkoxy)-C1-C4 alkyl radical; a C1-C4 aminoalkyl radical; a C1-C4 aminoalkyl radical whose amine is mono- or disubstituted by a C1-C4 alkyl radical, by an acetyl radical, by a C1-C4 monohydroxyalkyl radical or by a C2-C4 polyhydroxyalkyl radical; a (C1-C4 alkyl)-C1-C4 thioalkyl radical, a monohydroxy(C1-C4 alkyl)-C1-C4 thioalkyl radical; a polyhydroxy(C2-C4 alkyl)-C1-C4 alkyl radical; a C1-C4 carboxyalkyl radical; a (C1-C4 alkoxy)-C1-C4 thiocarbonylalkyl radical or a C1-C4 acetylaminoalkyl radical; a C1-C4 cyanoalkyl radical; a C1-C4 trifluoroalkyl radical; a C1-C4 haloalkyl radical; a C1-C4 phosphoalkyl radical, or a C1-C4 sulphoalkyl radical;
R2 and R3, which are identical or different, represent a hydrogen or halogen atom; a group Z; a group xe2x80x94NHxe2x80x94Z; a C1-C4 alkyl radical; a carboxyl radical; a (C1-C4 alkoxy)carbonyl radical or a formyl radical;
R4 and R5, which are identical or different, represent a hydrogen or halogen atom; a group Z; a group xe2x80x94NHxe2x80x94Z; a C1-C4 alkyl radical; a C1-C4 alkoxy radical; an acetylamino radical; a C1-C5 monohydroxyalkyl radical; a C2-C4 polyhydroxyalkyl radical; a (C1-C4 alkoxy)-C1-C4 alkyl radical; a thiophene radical; a furan radical; a phenyl radical; an aralkyl radical in which the alkyl moiety is C1-C4; a phenyl radical or aralkyl radical in which the alkyl moiety is C1-C4, each substituted by a halogen atom, by a C1-C4 alkyl radical, by a trifluoromethyl radical, by a C1-C4 alkoxy radical, by an amino radical or by an amino radical which is mono- or disubstituted by a C1-C4 alkyl radical; a (C1-C4 alkyl)-C1-C4 aminoalkyl radical or a di(C1-C4 alkyl)-C1-C4 aminoalkyl radical;
Z is selected from the unsaturated cationic groups of formulae (II) and (III) below and the saturated cationic groups of formula (IV) below:
in which: 
D is a linker which represents an alkyl chain containing preferably 1 to 14 carbon atoms, which is linear or branched and can be interrupted by one or more heteroatoms such as oxygen, sulphur or nitrogen atoms and can be substituted by one or more hydroxyl or C1-C6 alkoxy radicals and can carry one or more ketone functional groups;
the ring members E, G, J, L and M, which are identical or different, represent a carbon, oxygen, sulphur or nitrogen atom;
n is an integer of between 0 and 4 inclusive;
m is an integer of between 0 and 5 inclusive;
the radicals R, which are identical or different, represent a group Z, a halogen atom, a hydroxyl radical, a C1-C6 alkyl radical, a C1-C6 monohydroxyalkyl radical, a C2-C6 polyhydroxyalkyl radical, a nitro radical, a cyano radical, a C1-C6 cyanoalkyl radical, a C1-C6 alkoxy radical, a tri(C1-C6 alkyl)silyl-C1-C6 alkyl radical, an amido radical, an aldehydo radical, a carboxyl radical, a C1-C6 alkylcarbonyl radical, a thio radical, a C1-C6 thioalkyl radical, a (C1-C6 alkyl)thio radical, an amino radical, an amino radical protected by a (C1-C6 alkyl)carbonyl, carbamyl or (C1-C6 alkyl)sulphonyl radical; a group NHRxe2x80x3 or NRxe2x80x3Rxe2x80x2xe2x80x3 in which Rxe2x80x3 and Rxe2x80x2xe2x80x3, which are identical or different, represent a C1-C6 alkyl radical, a C1-C6monohydroxyalkyl radical or a C2-C6 polyhydroxyalkyl radical;
R6 represents a C1-C6 alkyl radical, a C1-C6 monohydroxyalkyl radical, a C2-C6 polyhydroxyalkyl radical, a C1-C6 cyanoalkyl radical, a tri(C1-C6 alkyl)silyl-C1-C6 alkyl radical, a (C1-C6 alkoxy)-C1-C6 alkyl radical, a C1-C6 carbamylalkyl radical, a (C1-C6 alkyl)-C1-C6 carboxyalkyl radical, a benzyl radical or a group Z of formula (II), (III) or (IV) as defined above;
R7, R8 and R9, which are identical or different, represent a C1-C6 alkyl radical, a C1-C6 monohydroxyalkyl radical, a C2-C6 polyhydroxyalkyl radical, a (C1-C6 alkoxy)-C1-C6 alkyl radical, a C1-C6 cyanoalkyl radical, an aryl radical, a benzyl radical, a C1-C6 amidoalkyl radical, a tri(C1-C6 alkyl)silyl-C1-C6 alkyl radical or a C1-C6 aminoalkyl radical whose amine is protected by a (C1-C6 alkyl)carbonyl, carbamyl or (C1-C6 alkyl)sulphonyl radical; where two of the radicals R7, R8 and R9 may also form, together with the nitrogen atom to which they are attached, a 5- or 6-membered saturated ring containing carbon or containing at least one additonal heteroatoms, such as, for example, a pyrrolidine ring, a piperidine ring, a piperazine ring or a morpholine ring, it being possible for the said ring to be unsubstituted or substituted by a halogen atom, a hydroxyl radical, a C1-C6 alkyl radical, a C1-C6 monohydroxyalkyl radical, a C2-C6 polyhydroxyalkyl radical, a nitro radical, a cyano radical, a C1-C6 cyanoalkyl radical, a C1-C6 alkoxy radical, a tri(C1-C6 alkyl)silyl-C1-C6 alkyl radical, an amido radical, an aldehydo radical, a carboxyl radical, a C1-C6 ketoalkyl radical, a thio radical, a C1-C6 thioalkyl radical, a (C1-C6 alkyl)thio radical, an amino radical, or an amino radical protected by a (C1-C6 alkyl)carbonyl, carbamyl or (C1-C6 alkyl)sulphonyl radical; one of the radicals R7, R8 and R9 may also represent a second group Z which is identical to or different from the first group Z;
R10 represents a C1-C6 alkyl radical; a C1-C6 monohydroxyalkyl radical; a C2-C6 polyhydroxyalkyl radical; an aryl radical; a benzyl radical; a C1-C6 aminoalkyl radical or a C1-C6 aminoalkyl radical whose amine is protected by a (C1-C6 alkyl)carbonyl, carbamyl or (C1-C6 alkyl)sulphonyl radical; a C1-C6 carboxyalkyl radical; a C1-C6 cyanoalkyl radical; a C1-C6 carbamylalkyl radical; a C1-C6 trifluoroalkyl radical; a tri(C1-C6 alkyl)silyl-C1-C6 alkyl radical; a C1-C6sulphonamidoalkyl radical; a (C1-C6-alkyl)carboxy-C1-C6 alkyl radical; a (C1-C6 alkyl)sulphinyl-C1-C6 alkyl radical; a (C1-C6 alkyl)sulphonyl-C1-C6 alkyl radical; a (C1-C6 alkyl)keto-C1-C6 alkyl radical; an N-(C1-C6 alkyl)carbamyl-C1-C6 alkyl radical; or an N-(C1-C6 alkyl)sulphonamido-C1-C6 alkyl radical;
x and y are integers equal to 0 or 1; with the following conditions:
in the unsaturated cationic groups of formula (II):
when x is 0, the linker D is attached to the nitrogen atom,
when x is 1, the linker D is attached to one of the ring members E, G, J or L,
y can adopt the value 1 only:
1) when the ring members E, G, J and L represent simultaneously a carbon atom and when the radical R6 is carried by the nitrogen atom of the unsaturated ring; or else
2) when at least one of the ring members E, G, J and L represents a nitrogen atom to which the radical R6 is attached;
in the unsaturated cationic groups of formula (III):
when x is 0, the linker D is attached to the nitrogen atom,
when x is 1, the linker D is attached to one of the ring members E, G, J, L or M,
y can adopt the value 1 only when at least one of the ring members E, G, J, L and M represents a divalent atom and when the radical R6 is carried by the nitrogen atom of the unsaturated ring;
in the cationic groups of formula (IV):
when x is 0, the linker is attached to the nitrogen atom which carries the radicals R7 to R9,
when x is 1, two of the radicals R7 to R9 form, conjointly with the nitrogen atom to which they are attached, a 5- or 6-membered saturated ring as defined above, and the linker D is carried by a carbon atom of the said saturated ring;
X represents a monovalent or divalent anion selected preferably from a halogen atom such as chlorine, bromine, fluorine or iodine, a hydroxide, a hydrogen sulphate or a C1-C6-alkyl sulphate such as, for example, a methyl sulphate or an ethyl sulphate;
with the proviso that:
the number of cationic groups Z of formula (II), (III) or (IV) is at least 1.
As indicated above, the colorations obtained with the oxidation dyeing composition in accordance with the invention can be intense and make it possible to obtain shades within a very wide range of colours. Moreover, they can exhibit excellent properties of resistance with respect to the action of various external agents (light, inclement weather, washing, permanent-waving, perspiration, friction). These properties can be particularly remarkable as regards, notably, the resistance of the colorations obtained with respect to the action of light, washing and perspiration.
In the formula (I) above the alkyl and alkoxy radicals can be linear or branched.
Among the rings of the unsaturated groups Z of formula (II) above, mention may be made in particular, by way of example, of pyrrole, imidazole, pyrazole, oxazole, thiazole and triazole rings.
Among the rings of the unsaturated groups Z of formula (III) above, mention may be made, in particular, by way of example, of pyridine, pyrimidine, pyrazine, oxazine and triazine rings.
Among the compounds of formula (I) above, mention may be made in particular of:
3-(4-hydroxy-1-methyl-1H-indol-5-ylmethyl)1-methylpyridinium methosuiphate:
4-(4-hydroxy-1-methyl-1H-indol-5-ylmethyl)-1-methylpyridinium methosulphate;
3-[3-(4-hydroxy-5-(1-methylpyridinium)4-ylmethylindol-1-yl)propyl]-1-methylimidazol-1-ium dimethosulphate;
4-(4-hydroxy-1-(2-hydroxyethyl)-1H-indol-5-ylmethyl)-1-methylpyridinium methosulphate;
3-[3-(4-hydroxy-5-(1-methylpyridinium)-5-ylmethyl-indol-1-yl)propyl]-1-methylimidazol-1-ium dimethosulphate;
3-[4-hydroxy-5-(1-methylpyrdinium)-3-ylmethyl-indol-1-ylmethyl]-1-methylpyiddinium dimethosulphate;
3-[3-(5-benzyl4-hydroxyindol-1-yl)propyl]-1-methyl-3H-imidazol-1-ium methosulphate;
[2-(4-hydroxy-1H-indol-3-yl)ethyl]trimethyl-ammonium methosulphate;
[2-(4-hydroxy-1-methyl-1H-indol-3-yl)ethyl]-trimethylammonium methosulphate;
(4-hydroxy-1-methyl-1H-indol-3-ylmethyl)-trimethylammonium methosulphate;
(4-hydroxy-1H-indol-3-ylmethyl)trimethylammonium methosulphate;
{3-[(4-hydroxy-1H-indole-2-carbonyl)amino]propyl}-trimethylammonium methosulphate;
{3-[(4-hydroxy-1-methyl-1H-indole-2-carbonyl)-amino]propyl}trimethylammonium methosulphate;
{3-[(4-hydroxy-5-methyl-1H-indole-2-carbonyl)-amino]propyl}trimethylammonium methosulphate;
{3-[(4-hydroxy-1,5-dimethyl-1H-indole-2-carbonyl)amino]propyl}trimethylammonium methosulphate;
3-{3-[(4-hydroxy-1H-indole-2-carbonyl)amino]-propyl}-1-methyl-3H-imidazol-1-ium methosulphate;
3-{3-[(4-hydroxy-1-methyl-1H-indole-2-carbonyl)-amino]propyl}-1-methyl-3H-imidazol-1-ium methosulphate;
3-{3-[(4-hydroxy-5-methyl-1H-indole-2-carbonyl)-amino]propyl}-1-methyl-3H-imidazol-1-ium methosulphate;
3-{3-[(4-hydroxy-1,5-dimethyl-1H-indole-2-carbonyl)amino]propyl}-1-methyl-3H-imidazol-1-ium methosulphate;
{3-[(4-hydroxy-1H-indole-6-carbonyl)amino]propyl}-trimethylammonium monochioride;
{3-[(4-hydroxy-1-methyl-1H-indole-6-carbonyl)-amino]propyl}trimethylammonium monochloride; and their addition salts with an acid.
The compounds of formula (I) in accordance with the invention can be readily obtained in accordance with well-known methods of the prior art such as, for example, in accordance with the preparation process described in the patent application FR-A-2 736 640, the disclosure of which is incorporated by reference herein, followed by a conventional final quaternization step.
The invention additionally provides for the use of the compounds of formula (I) in accordance with the invention as a coupler for the oxidation dyeing of keratinous fibers and, in particular, of human keratinous fibers such as the hair.
The invention also provides a composition for the oxidation dyeing of keratinous fibers and, in particular, of human keratinous fibers such as the hair, characterized in that it comprises, in a medium appropriate for dyeing, at least one compound of formula (I) in accordance with the invention.
The compound or compounds of formula (I) in accordance with the invention and/or its or their addition salt or salts with an acid represents or represent preferably from 0.0005 to 12% by weight, approximately, of the total weight of the dyeing composition, and, more preferably still, from 0.005 to 6% by weight, approximately, of this weight.
In accordance with one preferred embodiment of the invention, the dyeing composition additionally includes one or more oxidation bases which can be selected from the oxidation bases conventionally used in oxidation dyeing and among which mention may be made in particular of para-phenylenediamines, bisphenylalkylenediamines, para-aminophenols, ortho-aminophenols and heterocyclic bases.
Among the para-phenylenediamines, mention may be made more particularly, by way of example, of para-phenylenediamine, para-tolylenediamine, 2-chloro-para-phenylenediamine, 2,3-dimethyl-para-phenylenediamine, 2,6-dimethyl-para-phenylenediamine, 2,6-diethyl-para-phenylenediamine, 2,5-dimethyl-para-phenylenediamine, N,N-dimethyl-para-phenylenediamine, N,N-diethyl-para-phenylenediamine, N,N-dipropyl-para-phenylenediamine, 4-amino-N,N-diethyl-3-methylaniline, N,N-bis(xcex2-hydroxyethyl)-para-phenylenediamine, 4-N,N-bis(xcex2-hydroxyethyl)amino-2-methylaniline, 4-N,N-bis(xcex2-hydroxyethyl)amino-2-chloroaniline, 2-xcex2-hydroxyethyl-para-phenylenediamine, 2-fluoro-para-phenylenediamine, 2-isopropyl-para-phenylenediamine, N-(xcex2-hydroxypropyl)-para-phenylenediamine, 2-hydroxymethyl-para-phenylenediamine, N,N-dimethyl-3-methyl-para-phenylenediamine, N-ethyl-N-(xcex2-hydroxyethyl)-para-phenylenediamine, N-(xcex2,y-dihydroxypropyl)para-phenylenediamine, N-(4xe2x80x2-aminophenyl)-para-phenylenediamine, N-phenyl-para-phenylenediamine, 2-xcex2-hydroxyethyloxy-para-phenylenediamine, 2-xcex2-acetylaminoethyloxy-para-phenylenediamine, N-(xcex2-methoxyethyl)-para-phenylenediamine and their addition salts with an acid.
Among the abovementioned para-phenylenediamines, very particular preference is given to para-phenylenediamine, para-tolylenediamine, 2-isopropyl-para-phenylenediamine, 2-xcex2-hydroxyethyl-para-phenylenediamine, 2-xcex2-hydroxyethyloxy-para-phenylenediamine, 2,6-dimethyl-para-phenylenediamine, 2,6-diethyl-para-phenylenediamine, 2,3-dimethyl-para-phenylenediamine, N,N-bis(xcex2-hydroxyethyl)-paraphenylenediamine, 2-chloro-para-phenylenediamine, 2-xcex2-acetylaminoethyloxy-para-phenylenediamine, and their addition salts with an acid.
Among the bisphenylalkylenediamines, mention may be made, more particularly, by way of example, of N,Nxe2x80x2-bis(xcex2-hydroxyethyl)-N,Nxe2x80x2-bis(4xe2x80x2-aminophenyl)-1,3-diaminopropanol, N,Nxe2x80x2-bis(xcex2-hydroxyethyl)-N,Nxe2x80x2-bis(4xe2x80x2-aminophenyl)ethylenediamine, N,Nxe2x80x2-bis(4-aminophenyl)tetramethylenediamine, N,Nxe2x80x2-bis(xcex2-hydroxyethyl)-N,Nxe2x80x2-bis(4-aminophenyl)tetramethylene-diamine, N,Nxe2x80x2-bis(4-methylaminophenyl)tetramethylene-diamine, N, Nxe2x80x2-bis(ethyl)-N,Nxe2x80x2-bis(4xe2x80x2-amino-3xe2x80x2-methylphenyl)ethylenediamine, 1,8-bis(2,5-diaminophenoxy)-3,5-dioxaoctane, and their addition salts with an acid.
Among the para-aminophenols, mention may be made more particularly, by way of example, of para-aminophenol, 4-amino-3-methylphenol, 4-amino-3-fluorophenol, 4-amino-3-hydroxymethylphenol, 4-amino-2-methylphenol, 4-amino-2-hydroxymethylphenol, 4-amino-2-methoxymethylphenol, 4-amino-2-aminomethylphenol, 4-amino-2(xcex2-hydroxyethylaminomethyl)phenol, 4-amino-2-fluorophenol, and their addition salts with an acid.
Among the ortho-aminophenols, mention may be made more particularly, by way of example, of 2-aminophenol, 2-amino-5-methylphenol, 2-amino-6-methylphenol, 5-acetamido-2-aminophenol, and their addition salts with an acid.
Among the heterocyclic bases, mention may be made more particularly, by way of example, of pyridine derivatives, pyrimidine derivatives and pyrazole derivatives.
Among the pyridine derivatives, mention may be made more particularly of the compounds described, for example, in the patents GB 1 026 978 and GB 1 153 196, the disclosures of each which are incorporated by reference herein, such as 2,5-diaminopyridine, 2-(4-methoxyphenyl)amino-3-aminopyridine, 2,3-diamino-6-methoxypyridine, 2-(xcex2-methoxyethyl)amino-3-amino-6-methoxypyridine, 3,4-diaminopyridine, and their addition salts with an acid.
Among the pyrimidine derivatives, mention may be made more particularly of the compounds described, for example, in the German patent DE 2 359 399 or Japanese patents JP 88-169 571 and JP 91-10659 or patent application WO 96/15765, the disclosures of each which are incorporated by reference herein, such as 2,4,5,6-tetraaminopyrimidine, 4-hydroxy-2,5,6-triaminopyrimidine, 2-hydroxy-4,5,6-triaminopyrimidine, 2,4-dihydroxy-5,6-diaminopyrimidine, 2,5,6-triaminopyrimidine, and the pyrazolo-pyrimidine derivatives such as those mentioned in the patent application FR-A-2 750 048, the disclosure of which is incorporated by reference herein, and among which mention may be made of pyrazolo[1,5-a]pyrimidine-3,7-diamine; 2,5-dimethylpyrazolo[1,5-a]pyrimidine-3,7-diamine; pyrazolo[1,5-a]pyrimidine-3-5-diamine; 2,7-dimethylpyrazolo[1,5-a]pyrimidine-3,5-diamine; 3-aminopyrazolo[1,5-a]pyrimidin-7-ol; 3-aminopyrazolo[1,5-a]pyrimidin-5-ol; 2-(7-aminopyrazolo[1,5-a]pyrimidin-3-ylamino)ethanol, 2-[(3-aminopyrazolo[1,5-a]pyrimidin-7-yl)-(2-hydroxyethyl)amino]ethanol, 2-[(7-aminopyrazolo[1,5-a]pyrimidin-3-yl)-(2-hydroxyethyl)amino]ethanol, 5,6-dimethylpyrazolo[1,5-a]pyrimidine-3,7-diamine, 2,6-dimethylpyrazolo[1,5-a]pyrimidine-3,7-diamine, 2,5,N7,N7-tetramethylpyrazolo[1,5-a]pyrimidine-3,7-diamine, and their addition salts and their tautomeric forms, when a tautomeric equilibrium exists, and their addition salts with an acid.
Among the pyrazole derivatives, mention may be made more particularly of the compounds described in the patents DE 3 843 892, DE 4 133 957 and patent applications WO 94/08969, WO 94/08970, FR-A-2 733 749 and DE 195 43 988, the disclosures of each which are incorporated by reference herein, such as 4,5-diamino-1-methylpyrazole, 3,4-diaminopyrazole, 4,5-diamino-1-(4xe2x80x2-chlorobenzyl)pyrazole, 4,5-diamino-1,3-dimethylpyrazole, 4,5-diamino-3-methyl-1-phenylpyrazole, 4,5-diamino-1-methyl-3-phenylpyrazole, 4-amino-1,3-dimethyl-5-hydrazinopyrazole, 1-benzyl4,5-diamino-3-methylpyrazole, 4,5-diamino-3-tert-butyl-1-methylpyrazole, 4,5-diamino-1-tert-butyl-3-methylpyrazole, 4,5-diamino-1(xcex2-hydroxyethyl)-3-methylpyrazole, 4,5-diamino-1-ethyl-3-methylpyrazole, 4,5-diamino-1-ethyl-3-(4xe2x80x2-methoxyphenyl)pyrazole, 4,5-diamino-1-ethyl-3-hydroxymethylpyrazole, 4,5-diamino-3-hydroxymethyl-1-methylpyrazole, 4,5-diamino-3-hydroxymethyl-1-isopropylpyrazole, 4,5-diamino-3-methyl-1-isopropylpyrazole, 4-amino-5-(2xe2x80x2-aminoethyl)amino-1,3-dimethylpyrazole,3,4,5-triaminopyrazole, 1-methyl-3,4,5-triaminopyrazole, 3,5-diamino-1-methyl-4-methylaminopyrazole, 3,5-diamino-4-(xcex2-hydroxyethyl)amino-1-methylpyrazole, and their addition salts with an acid.
When they are used, these oxidation bases represent preferably from 0.0005 to 12% by weight, approximately, of the total weight of the dyeing composition, and still more preferably from 0.005 to 6% by weight, approximately, of this weight.
In addition to the compound or compounds of formula (I) above, the dyeing composition in accordance with the invention may also include at least one additional coupler which can be selected from the couplers used conventionally in oxidation dyeing and among which mention may be made in particular of meta-phenylenediamines meta-aminophenols, meta-diphenols and heterocyclic couplers such as, for example, indole derivatives, indoline derivatives, pyridine derivatives and pyrazolones, and their addition salts with an acid.
These couplers are selected more particularly from 2-methyl-5-aminophenol, 5-N-(xcex2-hydroxyethyl)amino-2-methylphenol, 3-aminophenol, 1,3-dihydroxybenzene, 1,3-dihydroxy-2-methylbenzene, 4-chloro-1,3-dihydroxybenzene, 2,4-diamino-1-(xcex2-hydroxyethyloxy)-benzene, 2-amino-4-(xcex2-hydroxyethylamino)-1-methoxybenzene, 1,3-diaminobenzene, 1,3-bis(2,4-diaminophenoxy)propane, sesamol, xcex1-naphthol, 6-hydroxy-indole, 4-hydroxyindole, 4-hydroxy-N-methylindole, 6-hydroxyindoline, 2,6-dihydroxy-4-methylpyridine, 1H-3-methylpyrazol-5-one, 1-phenyl-3-methylpyrazol-5-one, and their addition salts with an acid.
When they are present, these couplers represent preferably from 0.0001 to 10% by weight, approximately, of the total weight of the dyeing composition, and still more preferably from 0.005 to 5% by weight, approximately, of this weight.
Generally speaking, the addition salts with an acid which can be used in the context of the dyeing compositions of the invention (compounds of formula (I), oxidation bases and additional couplers) are selected in particular from hydrochlorides, hydrobromides, sulphates, citrates, succinates, tartrates, lactates and acetates.
The medium appropriate for dyeing (or vehicle) generally is water or a mixture of water and at least one organic solvent for solubilizing the compounds which would not be sufficiently soluble in water. By way of organic solvent, mention may be made, for example, of C1-C4 lower alkanols, such as ethanol and isopropanol; glycerol; glycols and glycol ethers, such as 2-butoxyethanol, propylene glycol, propylene glycol monomethyl ether, diethylene glycol monoethyl ether and monomethyl ether, and aromatic alcohols, such as benzyl alcohol or phenoxyethanol, similar products, and mixtures thereof.
The solvents can be present in proportions of preferably between 1 and 40% inclusive by weight, approximately, relative to the total weight of the dyeing composition, and still more preferably between 5 and 30% inclusive by weight, approximately.
The pH of the dyeing composition according to the invention is generally between 3 and 12 inclusive, approximately, and preferably between 5 and 11 inclusive, approximately. It can be adjusted to the desired value by means of acidifying or basifying agents which are commonly employed in the dyeing of keratinous fibers.
Among the acidifying agents, mention may be made, by way of example, of mineral acids or organic acids such as hydrochloric acid, ortho-phosphoric acid, sulphuric acid, carboxylic acids such as acetic acid, tartaric acid, citric acid and lactic acid, and sulphonic acids.
Among the basifying agents, mention may be made, by way of example, of aqueous ammonia, alkali metal carbonates, alkanolamines such as mono-, di- and triethanolamines and their derivatives, sodium hydroxide or potassium hydroxide, and the compounds of formula (V) below: 
in which W is a propylene radical optionally substituted by a hydroxyl group or a C1-C6 alkyl radical; and R11, R12, R13 and R14, which are identical or different, represent a hydrogen atom or a C1-C6 alkyl or C1-C6 hydroxyalkyl radical.
The oxidation dyeing compositions in accordance with the invention may also include at least one direct dye, in particular for modifying the shades or enriching them with glints.
The dyeing composition in accordance with the invention may also include various adjuvants which are conventionally employed in hair-dyeing compositions, such as anionic, cationic, nonionic, amphoteric or zwitterionic surfactants or mixtures thereof, anionic, cationic, nonionic, amphoteric or zwitterionic polymers or mixtures thereof, mineral or organic thickeners, antioxidants, penetrants, sequestrants, perfumes, buffers, dispersants, conditioning agents such as, for example, volatile or nonvolatile silicones, modified or otherwise, film formers, ceramides, preservatives and opacifiers.
The person skilled in the art will of course take care to select this or these optional complementary compounds such that the advantageous properties associated intrinsically with the oxidation dyeing composition in accordance with the invention are not, or not substantially, adversely affected by the intended addition or additions.
The dyeing composition according to the invention can be presented in a variety of forms, such as in the form of liquids, creams, gels or any other form appropriate for carrying out dyeing of keratinous fibers and, in particular, of human hair.
The invention also provides a method of oxidation-dyeing keratinous fibers and, in particular, human keratinous fibers such as the hair, employing the dyeing composition as defined above.
In accordance with this method, at least one dyeing composition as defined above is applied to the fibers, the colour being revealed at an acidic, neutral or alkaline pH with the aid of an oxidizing agent which is added to the dyeing composition right at the time of use or which is present in an oxidizing composition which is applied simultaneously or sequentially.
In accordance with a preferred embodiment of the dyeing method of the invention, the above-described dyeing composition is preferably mixed, at the time of use, with an oxidizing composition comprising, in a medium appropriate for dyeing, at least one oxidizing agent which is present in an amount sufficient to develop a coloration. The mixture obtained is subsequently applied to the keratinous fibers and is left to act for from 3 to 50 minutes, approximately, preferably from 5 to 30 minutes, approximately, after which the fibers are rinsed, washed with shampoo, rinsed again and dried.
The oxidizing agent can be selected from the oxidizing agents which are conventionally used for the oxidation dyeing of keratinous fibers, and among which mention may be made of hydrogen peroxide, urea peroxide, alkali metal bromates, persalts such as perborates and persulphates, and enzymes such as peroxidases, laccases and oxidoreductases having 2 electrons. Hydrogen peroxide is particularly preferred.
The pH of the oxidizing composition comprising the oxidizing agent as defined above is such that, after mixing with the dyeing composition, the pH of the resultant composition that is applied to the keratinous fibers varies preferably between 3 and 12 inclusive, approximately, and still more preferably between 5 and 11 inclusive. It is adjusted to the desired value by means of acidifying or basifying agents which are commonly employed in dyeing keratinous fibers, such agents being as defined above.
The oxidizing composition as defined above may also include various adjuvants which are conventionally employed in hair-dyeing compositions, such adjuvants being as defined above.
The composition which is finally applied to the keratinous fibers may be presented in various forms, such as in the form of liquids, creams, gels or any other form appropriate for carrying out dyeing of keratinous fibers and, in particular, of human hair.
The invention also provides a multi-compartment dyeing device or kit, or any other packaging system having two or more compartments, of which a first compartment contains the dyeing composition as defined above and a second compartment contains the oxidizing composition as defined above. These devices can be equipped with a means allowing the desired mixture to be delivered to the hair, such as the devices described in the patent FR-2 586 913, the disclosure of which is incorporated by reference herein, in the name of the applicant.